Patent GB-766566-A (GB)
Title: Preparation of bi-heterocyclic phosphorus containing compounds
IPC: C07F9/6574
Filed: 1954-03-31
Abstract: The invention comprises heterocyclic phosphorus compounds of the formula <FORM:0766566/IV(b)/1> wherein R, R1, R2, R3 and R4 each represent a hydrogen atom or an alkyl group, X designates a divalent substituted hydrocarbon residue having two terminal oxy groups respectively connected with different phosphorus atoms, said residue being derived from an alkylene glycol, a polyalkylene glycol, a dihydric phenol, a biphenol, a bicresol, a diphenylolalkane or a ditolylolalkane, and n is 0 or 1.  The novel compounds may be prepared by reacting an unsubstituted or alkyl substituted 2-halo-2-oxo-1,3,2-dioxaphospholane or a corresponding 2-halo-2-oxo-1,3,2-dioxaphosphorinane with an alkylene glycol, a polyalkylene glycol, a dihydric phenol, a biphenol, a bicresol, a diphenylolalkane, a ditolylolalkane, or an alkali metal salt of such compounds.  The reaction is preferably effected in the presence of a hydrogen halide sequestering agent such as pyridine and other tertiary amines, and a volatile inert solvent at temperatures between - 30 DEG  C. and 120 DEG  C.  Suitable dihydroxy compounds are specified.  The novel compounds may also be prepared by first reacting a phosphoryl halide with one of the said dihydroxy compounds, or an alkali metal salt thereof, to form a tetrahalodiphosphate ester which is then reacted with either a 1,2-alkylene glycol or a 1,3-alkylene glycol.  Examples describe the preparation of (1) 2,21 - (1,3 - butanediol) bis - (4 - methyl - 2-oxo - 1,3,2 - dioxaphosphorinane) from 2-chloro - 4 - methyl - 2 - oxo - 1,3,2 - dioxaphosphorinane and 1,3 - butanediol; (2) 2,21 - (2-ethyl - 1,3 - hexanediol) - bis - (5 - ethyl - 4-propyl - 2 - oxo - 1,3,2 - dioxaphosphorinane from 2-chloro - 5 - ethyl - 4 - propyl - 2 - oxo-1,3,2 - dioxaphosphorinane and 2 - ethyl - 1,3-hexanediol; (3) 2,21 - (2 - butoxymethyl - 2,4-dimethyl - 1,5 - pentanediol) - bis - (4 - methyl - 2 - oxo - 1,3,2 - dioxaphospholane) from 2-chloro - 4 - methyl - 2 - oxo - 1,3,2 - dioxaphospholane and 2 - butoxymethyl - 2,4 - dimethyl-1,5 - pentanediol; (4) 2,21 - diethyleneglycol bis(5 - ethyl - 4 - propyl - 2 - oxo - 1,3,2 - dioxaphosphorinane from diethylene glycol tetrachlorodiphosphate and 2 - ethyl - 1,3 - hexanediol; (5) 2,21 - triethylene glycol - bis - (5-ethyl - 4 - propyl - 2 - oxo - 1,3,2 - dioxaphosphorinane) from triethylene glycol tetrachlorodiphosphate and 2 - ethyl - 1,3 - hexanediol; (6) 2,21 - triethylene glycol bis - (5 - ethyl - 4-propyl - 2 - oxo - 1,3,2 - dioxaphosphorinane) from 2 - chloro - 5 - ethyl - 4 - propyl - 2 - oxo-1,3,2 - dioxaphosphorinane and triethylene glycol; (7) 2,21 - (p,p1- isopropylidenediphenoxy) bis - (5 - ethyl - 4 - propyl - 2 - oxo - 1,3, 2-dioxaphosphorinane) from 2 - chloro - 5 - ethyl-4 - propyl - 2 - oxo - 1,3,2 - dioxaphosphorinane and the dipotassium salt of p,p1-isopropylidene diphenol; the reaction of 2-halo-2-oxo-1,3,2-dioxaphosphorinane with (i) hydroquinone to give 2,21 - (p - phenylenedioxy) bis - (2 - oxo-1,3,2 - dioxaphosphorinane); and (ii) with p,p1-biphenol to give 2,21 - (p,p1 - biphenoxy) bis-(2 - oxo - 1,3,2 - dioxaphosphorinane) is also mentioned.  The products are good solvents and plasticizers for synthetic resins and are useful as assistants in the textile industry.